CN103969947A - Alkaline developable photosensitive resin composition, dry film and cured product thereof, and printed circuit board formed by using alkaline developable photosensitive resin composition - Google Patents
Alkaline developable photosensitive resin composition, dry film and cured product thereof, and printed circuit board formed by using alkaline developable photosensitive resin composition Download PDFInfo
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- CN103969947A CN103969947A CN201310038669.5A CN201310038669A CN103969947A CN 103969947 A CN103969947 A CN 103969947A CN 201310038669 A CN201310038669 A CN 201310038669A CN 103969947 A CN103969947 A CN 103969947A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The present invention provides an alkaline developable photosensitive resin composition, a dry film and a cured product thereof, and a printed circuit board formed by using the alkaline developable photosensitive resin composition, wherein coated film overflow resistance, film floating resistance, adhesion with copper in through hole (short for TH), and cracking resistance of the photosensitive resin composition are excellent. The photosensitive resin composition is characterized by comprising (A) a carboxyl-containing resin, (B) a photopolymerization initiator, (C) a dilution solvent, (D) a compound having more than two ethylenic unsaturated groups in one molecule, and (E) talc, wherein the (A) carboxyl-containing resin contains a carboxyl-containing resin (A-1) obtained by carrying out a reaction of an epoxy esterification product and a saturated or unsaturated polybasic acid anhydride (c), the epoxy esterification product is obtained by carrying out an esterification reaction of at least a bisphenol type epoxy compound (a) and an unsaturated carboxylic acid (b), and the (E) talc content is more than 10 wt% of the total amount and is less than 60 wt% of the total amount.
Description
Technical field
The present invention relates to photosensitive polymer combination and the solidfied material thereof of alkali developable applicable in the formation of solder resist of printed circuit board (PCB) etc., be particularly related to while development by ultraviolet exposure and with dilute alkaline aqueous solution, can form image, especially resistance to blast hole, resistance to cavity and with TH(through hole) in copper adaptation and resistance to cracking line excellence, can obtain photosensitive polymer combination and its solidfied material of the alkali developable of cured coating film and printed circuit board (PCB).
Background technology
From high precision, highdensity viewpoint, now, in the solder resist of the civilian printed circuit board (PCB) of a part and nearly all industrial printed circuit board (PCB), thereby after using ultraviolet exposure, development forms image and solidifies the liquid developable solder flux of (main solidifying) by heat and irradiation completely.In addition,, from the misgivings of environmental problem, use dilute alkaline aqueous solution to become main flow as the liquid solder resist of alkali developable of developer solution.As the solder resist of the alkali developable of such use dilute alkaline aqueous solution, for example, the liquid solder mask composition that the active energy ray-curable resin, Photoepolymerizationinitiater initiater, thinning agent and the epoxy compound that are obtained by addition multi-anhydride on the resultant of reaction at phenolic varnish type epoxy compound and unsaturated monocarboxylic described in patent documentation 1 forms is widely used.
But, for example use in the situation of described existing liquid solder mask composition with the method being directly filled on the circuit board with TH, the solder resist film of formation has the phenomenon (being designated hereinafter simply as " cavity ") that while easily appearing at solder leveling (Solder leveller), TH periphery floats; Or in the rear problem of solidifying, be filled in when solder leveling the phenomenon (being designated hereinafter simply as " blast hole ") that the film in TH overflows.
Special in the Asia with headed by China, with the circuit board of the mode of whole through holes of the such circuit board of liquid solder mask composition filling copper TH circuit board be main flow, need to develop the solder mask composition of the problem of tackling described cavity, blast hole.The well-known liquid solder mask composition that has bisphenol type resin that being used in combination described in for example patent documentation 2 or patent documentation 3 have photonasty and alkali-developable, cresols phenolic varnish type resin, copoly type resin and obtain.
On the other hand, printed circuit board (PCB) uses year by year compactization and has the printed circuit board (PCB) in various apertures.In more than 500 printed circuit board (PCB) of Φ, use the solder mask composition with described resistance to cavity and resistance to blast hole that the not enough unfavorable condition cracking of adaptation by the interface of the copper in TH and solder mask composition occurs sometimes if in aperture be wherein.Fig. 1 has expressed the shape of this unfavorable condition.Such unfavorable condition likely can cause following new unfavorable condition: in the time that solder flux (flax) is coated with, solder flux easily enters in TH, solder flux is back to the opposing face of solder flux coated face, pollute residual flux in substrate surface, TH and in the time that aftertreatment flattens, produce expansion, therefore expectation develop a kind of resistance to blast hole, resistance to cavity and with TH in the adaptation of copper and the solder mask composition of resistance to cracking line excellence.
Patent documentation 1: No. 61-243869, Japanese kokai publication sho
Patent documentation 2: No. 2008-116813, TOHKEMY
Patent documentation 3: No. 2003-059975, international publication number
Patent documentation 4: No. 2002-256060, TOHKEMY
Summary of the invention
the problem that invention will solve
The object of the invention is to, provide resistance to blast hole, resistance to cavity and with TH in copper adaptation and resistance to cracking line excellence, can obtain photosensitive polymer combination and its solidfied material and the printed circuit board (PCB) of the alkali developable of cured coating film.Fundamental purpose of the present invention is, provide with TH in copper adaptation and resistance to cracking line excellence, be suitable for the photosensitive polymer combination of the alkali developable of the solder mask composition of use in printed circuit board.
More specifically, the object of the invention is to, the desired resistance to blast hole of solder resist not only, resistance to cavity excellence but also the adaptation of copper and the photosensitive polymer combination of resistance to cracking line excellence in not enough and TH are in the prior art provided.
for the scheme of dealing with problems
The inventor etc. further investigate repeatedly for solving described problem, found that, alkali development-type photosensitive resin composition as described below can solve described problem, thereby complete the present invention, described alkali development-type photosensitive resin composition is characterised in that, contain (A) containing carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) diluting solvent, (D) in a part, there is the compound of plural ethene unsaturated group and (E) talcum, contain carboxy resin as (A), the esterification product that contains the epoxy radicals that makes at least one bisphenol type epoxy compound (a) carry out esterification with unsaturated carboxylic acid (b) and to generate react with saturated or unsaturated multi-anhydride (c) and obtain containing carboxy resin (A-1), and more than 10 % by weight that (E) containing ratio of talcum is total amount and below 60 % by weight.
, alkali development-type photosensitive resin composition of the present invention is characterised in that, contain (A) containing carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) diluting solvent, (D) in a part, there is the compound of plural ethene unsaturated group and (E) talcum, contain carboxy resin as (A), the esterification product that contains the epoxy radicals that makes at least one bisphenol type epoxy compound (a) and unsaturated carboxylic acid (b) carry out esterification generation react with saturated or unsaturated multi-anhydride (c) and obtain containing carboxy resin (A-1), and more than 10 % by weight that (E) containing ratio of talcum is total amount and below 60 % by weight.
In addition, be preferably TH filling purposes.
In addition, preferably contain (F) filler except (E) talcum.
In addition preferably contain, (G) Thermocurable composition.
In addition, be preferably coated on copper and use.
In addition, dry film of the present invention is characterised in that, is coated with described alkali development-type photosensitive resin composition and is also dried and obtains in carrier film.
In addition, solidfied material of the present invention is characterised in that, following photocatalytic coating film is solidified and obtained, and described film is: described alkali development-type photosensitive resin composition is coated on copper and the dry film obtaining; Maybe this photosensitive polymer combination is coated in carrier film and dry, by the dry film lamination of gained photo-curable on copper and the film obtaining.
In addition, printed circuit board (PCB) of the present invention is characterised in that, carries out heat curing and obtain after following photocatalytic coating film is solidified, and described film is: described alkali development-type photosensitive resin composition is coated on base material and the dry film obtaining; Maybe this photosensitive polymer combination is coated in carrier film and dry, by the dry film lamination of gained photo-curable on base material and the film obtaining.
The maximum technical characterictic of photosensitive polymer combination of the present invention is, contain carboxy resin as (A), the esterification product that contains the epoxy radicals that makes at least one bisphenol type epoxy compound (a) carry out esterification with unsaturated carboxylic acid (b) and to generate react with saturated or unsaturated multi-anhydride (c) and obtain containing carboxy resin (A-1), and (E) 10 % by weight that the containing ratio of talcum is total amount are above and below 60 % by weight.
Feature of the present invention based on such forms, there is the flexible described carboxy resin (A-1) that contains by use and contain carboxy resin as (A), and more than 10 % by weight that the containing ratio that makes (E) talcum is total amount and below 60 % by weight, can make the hardness of solidfied material soft, give its photosensitive polymer combination flexibility.Its result, cure shrinkage can relax rear photosensitive polymer combination when curing and solidify time, and, due to the flexibility of this photosensitive polymer combination, photosensitive polymer combination can be followed being cured of copper surface in TH well concavo-convexly, can prevent thus the crackle on the interface of copper in TH and photosensitive polymer combination.In addition, it is good that the mobility of alkali development-type photosensitive resin composition becomes, and in the time of printing, becomes good to the imbedibility in TH.
On the other hand, although the solder mask composition existing with resistance to cavity can obtain resistance to cavity, can not fully obtain with TH in the adaptation of copper.Its reason is, 3), silicon dioxide (Mohs value: 7) although existing solder mask composition contains described containing carboxy resin (A-1) and (F) filler, (F) filler is used as the barium sulphate that the Mohs value of yardstick of the hardness of mineral is high (Mohs value: conventionally.The yardstick of the hardness of Mohs value uses 1～10 round values, and numeral is larger, shows that the hardness of mineral is higher.Owing to using high barium sulphate, the silicon dioxide of Mohs value, therefore can not give described photosensitive polymer combination sufficient flexibility.Its result, the mitigation of rear cure shrinkage when curing becomes insufficient, the concavo-convex of copper surface that is difficult to fully follow in TH is cured, can not obtain fully with TH in the adaptation of copper.
As mentioned above, the sufficient flexibility deficiency of above-mentioned existing photosensitive polymer combination, be difficult to give with TH in the adaptation of copper.Therefore, in the present invention, be 1 by using Mohs value, in mineral, be (E) talcum of one of the most soft mineral, seek to improve aforesaid problem.
the effect of invention
Known as mentioned above, utilize the present invention, can provide with TH in photosensitive polymer combination and the solidfied material thereof of adaptation, resistance to blast hole, resistance to cavity and resistance to cracking line excellence of copper.
Brief description of the drawings
[Fig. 1] a represents that the copper of TH and film the abnormal figure such as do not peel off.B represents the copper of TH and the figure that film is peeled off.
description of reference numerals
1 China ink
2 bronze medals
3 base materials
Embodiment
Below, the each constituent in alkali development-type photosensitive resin composition of the present invention is described.
Alkali development-type photosensitive resin composition of the present invention is characterised in that and contains (E) talcum as essential composition, therefore first (E) talcum described.
(E) talcum
(E) talcum using in alkali development-type photosensitive resin composition of the present invention for improve with TH in adaptation and the resistance to cracking line of copper use.
As such (E) talcum, parent rock stone is any in magnesium carbonate, serpentine, silicon dioxide/silica-alumina, magnesium sediment, is the one of so-called silicate mineral, and shape can be that bulk can be also micro mist shape.Can carry out surface treatment also can not carry out.
Above and 60 % by weight of 10 % by weight that the compounding ratio of these (E) talcums is total amount are suitable below.When less than 10 % by weight, can not fully obtain with TH in adaptation and the resistance to cracking line of copper, while exceeding 60 % by weight, the mobility variation of alkali development-type photosensitive resin composition, to the imbedibility variation in TH, therefore not preferred when printing.
(A) containing carboxy resin
First, to describing as the carboxy resin (A-1) that contains obtaining containing esterification product carboxy resin (A), that at least one bisphenol type epoxy compound (a) and unsaturated carboxylic acid (b) carry out the epoxy radicals of esterification generation reacts with saturated or unsaturated multi-anhydride (c) of the present invention.
As at such at least one bisphenol type epoxy compound (a) containing using in the manufacture of carboxy resin (A-1), use on the alcohol hydroxyl group of bisphenol A-type or Bisphenol F type taking the compound that the epihalohydrin such as the amount addition chloropropylene oxide more than 1 equivalent obtains with respect to alcohol hydroxyl group 1 equivalent.
As the unsaturated carboxylic acid (b) of addition in the epoxy radicals to described bisphenol type epoxy compound, can list: the unsaturated dicarboxylic acid anhydride addition product of the hydroxy acryl acid esters such as acrylic acid, acrylic acid dimer, methacrylic acid, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, (methyl) acrylic acid phenyl glycidyl ester, (methyl) acrylic acid caprolactone addition product etc.Wherein particularly preferably acrylic acid, methacrylic acid.These monocarboxylic acids containing unsaturated group can be used alone or as a mixture.
As the saturated or unsaturated multi-anhydride (c) reacting with the alcohol hydroxyl group in the carboxylate being generated with the esterification of described unsaturated carboxylic acid by described bisphenol type epoxy compound, can list: aliphatics or the aromatic dicarboxylic anhydrides such as methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride.
In addition in the scope that, this use amount saturated or unsaturated multi-anhydride is preferably 45 ~ 120mgKOH/g at the acid number containing carboxy resin (A-1) obtaining, add.
Then, as other containing the object lesson of carboxy resin (A), be preferably the following compound of enumerating (for any in oligomer and polymkeric substance).
Can list:
(1) unsaturated carboxylic acid such as (methyl) acrylic acid with obtain except more than one compound copolymerization with unsaturated double-bond it contain carboxyl copolymer resins,
(2) at unsaturated carboxylic acids such as (methyl) acrylic acid and in the interpolymer of more than one compounds with unsaturated double-bond it, utilize (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters etc. has the addition ethene unsaturated group such as compound, (methyl) acrylic acid chloride of epoxy radicals and unsaturated double-bond as side chain, thus the photonasty obtaining containing carboxyl copolymer resins,
(3) make (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters etc. has the compound of epoxy radicals and unsaturated double-bond and reacts except unsaturated carboxylic acids such as the multipolymer of the compound with unsaturated double-bond it and, (methyl) acrylic acid, the secondary hydroxyl that makes to generate react with multi-anhydride and the photonasty that obtains contain carboxyl copolymer resins,
(4) make maleic anhydride etc. have that the acid anhydrides of unsaturated double-bond reacts with the compound except the multipolymer of the compound with unsaturated double-bond it and, (methyl) acrylic acid 2-hydroxyl ethyl ester etc. with hydroxyl and unsaturated double-bond and the photonasty that obtains containing carboxyl copolymer resins,
(5) make the reaction of multi-functional epoxy compound and unsaturated monocarboxylic, the hydroxyl that makes to generate react with saturated or unsaturated multi-anhydride and obtain contain carboxyl photoresist,
(6) after the hydroxyl polymer-containings such as polyvinyl alcohol derivative are reacted with saturated or unsaturated multi-anhydride, the carboxylic acid that makes to generate react with the compound in a part with epoxy radicals and unsaturated double-bond and the photosensitive resin of the hydroxyl that obtains and carboxyl,
(7) make to have in multi-functional epoxy compound, unsaturated monocarboxylic and a part at least one alcohol hydroxyl group and react with, saturated or unsaturated multi-anhydride with the reaction product of the compound of the reactive group except alcohol hydroxyl group of epoxy reaction and obtain containing carboxyl photoresist,
(8) the multifunctional oxetane compound that makes to have at least 2 oxetanes rings in a part reacts with unsaturated monocarboxylic, the primary hydroxyl in the modification oxetane resin that makes to obtain react with saturated or unsaturated multi-anhydride and obtain containing carboxyl photoresist and
(9) after polyfunctional epoxy resin is reacted with unsaturated monocarboxylic, make that multi-anhydride reaction obtains containing carboxy resin further with in molecule, have an oxirane ring react with the compound of more than one ethene unsaturated group and obtain contain carboxyl photoresist etc., but be not limited to these materials.
Particularly preferred material in illustrating as these is the carboxy resin that contains of described (2), (5), (7), (9).
It should be noted that, in this manual, (methyl) acrylate is the term of being referred to as acrylate, methacrylate and composition thereof, and other are similarly expressed too.
The carboxy resin (A) that contains as described above, owing to having multiple free carboxyls on the side chain of trunk polymer, therefore can utilize dilute alkaline aqueous solution to develop.
In addition, the above-mentioned acid number containing carboxy resin (A) is preferably the scope of 40 ~ 200mgKOH/g, the more preferably scope of 45 ~ 120mgKOH/g.While containing the not enough 40mgKOH/g of acid number of carboxy resin, being difficult to alkali develops, on the other hand, while exceeding 200mgKOH/g, can promote the dissolving of developer solution to exposure portion, therefore, it is thinner than needed that line becomes, sometimes be dissolved by the developing and peel off exposure portion and unexposed portion indistinction, be difficult to describe normal corrosion-resisting pattern, therefore not preferred.
In addition, the aforementioned weight-average molecular weight containing carboxy resin (A) is according to resin matrix and difference is preferably 2000～150000, more preferably 5000～100000 scope conventionally.When weight-average molecular weight less than 2000, sometimes to the coating of substrate, dried tack-free degradation, in addition, when the moisture-proof of the film after exposure worsens, develops sometimes, produce film minimizing, significantly variation of resolution.On the other hand, weight-average molecular weight exceedes at 150000 o'clock, and developability can significantly deteriorated, storage stability meeting variation sometimes.
This compounding amount containing carboxy resin (A) it is desirable to the scope into 20 ~ 60 quality % of whole compositions, is preferably 30 ~ 50 quality %.Compounding amount containing carboxy resin (A) is less than in the situation of described scope, therefore coating strength reduction is not preferred.On the other hand, therefore in the situation more than described scope, the viscosity of composition uprises or coating etc. reduces not preferred.
(B) Photoepolymerizationinitiater initiater
As Photoepolymerizationinitiater initiater (B) that can suitable use in alkali development-type photosensitive resin composition of the present invention, can list:
Benzoin and the benzoin alkylether classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether;
Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-[4-(4-benzoylphenyl sulfonyl)-2-methyl-2-(4-aminomethyl phenyl sulfonyl)] acetophenones such as propane-1-ketone;
2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-aminoacetophenone the classes such as butanone-1;
The Anthraquinones such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone;
2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, CTX, 2, the thioxanthene ketones such as 4-diisopropyl thioxanthones;
The ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal;
The benzophenones such as benzophenone or xanthene ketone;
Two (2,6-dimethoxy benzoyl) (2,4,4-tri-methyl-amyl) phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2,4, the acylphosphine oxide classes such as 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;
Various peroxides etc., can be used alone or in combination two or more these known conventional Photoepolymerizationinitiater initiaters.
As the preferred configuration of (B) Photoepolymerizationinitiater initiater, use 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1, as commercially available product, can list: the IRGACURE907 that Ciba-Geigy Company manufactures etc.
For the compounding ratio of these Photoepolymerizationinitiater initiaters (B), with respect to being that 0.01 ~ 30 mass parts is suitable containing carboxy resin (A) described in 100 mass parts, be preferably 5 ~ 25 mass parts.The use amount of Photoepolymerizationinitiater initiater is than in the few situation of described scope, the photo-curable variation of composition, on the other hand, in too much situation, therefore reduce not preferred as the characteristic of solder resist.
(C) organic solvent
For the organic solvent using in alkali development-type photosensitive resin composition of the present invention (C), for synthetic aforementioned containing carboxy resin (A), prepare composition or in order to adjust viscosity to be coated in substrate, carrier film, can be with an organic solvent.
As such organic solvent, can list: ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.More specifically, be the ketone such as MEK, cyclohexanone; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.Above-mentioned organic solvent can use separately or use with the form of two or more potpourris.
(D) in molecule, there is the compound of more than two ethene unsaturated group
The compound (D) in the molecule using in alkali development-type photosensitive resin composition of the present invention with more than two ethene unsaturated group is to carry out photocuring by irradiation active energy beam to make the aforementioned carboxy resin (A) that contains be insoluble to aqueous alkali or contribute to the aforementioned compound that is insoluble to aqueous alkali containing carboxy resin.As the object lesson of such compound, can list:
The acrylic acid hydroxy alkyl ester classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate;
Mono acrylic ester or the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol;
N,N-DMAA, N hydroxymethyl acrylamide, N, the acrylic amides such as N-dimethylamino propyl acrylamide;
Acrylic acid N, N-dimethylaminoethyl, acrylic acid N, the acrylic-amino alkyl esters such as N-dimethylamino propyl ester;
The multicomponent methacrylate class of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct or propylene oxide adduct etc.;
The esters of acrylic acid such as ethylene oxide adduct or propylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols;
The esters of acrylic acid of the glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester;
And melamine acrylate and the each methyl acrylic ester corresponding with aforesaid propylene acid esters at least any etc.
And then, can also list: the polyfunctional epoxy resins such as cresols phenolic resin varnish type epoxy resin are reacted with the acrylic acid Epocryl forming, the hydroxyl that further makes this Epocryl react epoxy amino formic ether acrylate compounds forming etc. with half carbamate (half urethane) compound of the diisocyanate such as hydroxy acrylate and isophorone diisocyanate such as pentaerythritol triacrylate.
Aforementioned containing carboxy resin (A) with respect to 100 mass parts, the compounding amount in such molecule with the compound (D) of more than two ethene unsaturated group expects to be the ratio of 5 ~ 100 mass parts, the more preferably ratio of 10 ~ 70 mass parts.Described compounding amount is with respect to containing described in 100 mass parts in the situation of carboxy resin (A) less than 5 mass parts, the photo-curable of the alkali development-type photosensitive resin composition obtaining reduces, be difficult to develop and form pattern by the postradiation alkali of active energy beam, therefore not preferred.On the other hand, while exceeding 100 mass parts, dissolubility reduction, the cured coating film of aqueous alkali are become fragile, therefore not preferred.
(F) filler
In order to improve the adaptation of the copper in thermotolerance and TH, alkali development-type photosensitive resin composition of the present invention can use (F) filler.
As such (F) filler, can list: the known conventional inorganic or organic fillers such as barium sulphate, barium titanate, silica powder, spherical silicon dioxide, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, glass fibre, carbon fiber, mica powder.(F) filler like this can carry out surface treatment also can not carry out surface treatment.
The compounding ratio of (F) filler is like this more than 0.01 % by weight of total amount and be suitable below 50 % by weight.When less than 0.01 % by weight, can not fully obtain with TH in adaptation and the thermotolerance of copper, while exceeding 50 % by weight, the mobility variation of alkali development-type photosensitive resin composition, to the imbedibility variation in TH, therefore not preferred in the time of printing.
(G) Thermocurable composition
In order to give thermotolerance and resistance to cracking line, in the alkali development-type photosensitive resin composition compounding molecule using in the present invention, there is the Thermocurable composition (G) of more than two reactive group (at least any (being designated hereinafter simply as ring-type (sulphur) ether) in ring-type ether and cyclic thioether base).
Thermocurable composition (G) is any or two kinds of plural compounds of group that have in molecule in three-membered ring, four-membered ring or pentacyclic ring-type ether or cyclic thioether base, for example, can list: the compound in molecule with more than at least two epoxy radicals is multi-functional epoxy compound (G-1), the compound in molecule with more than at least two oxetanyl is multifunctional oxetane compound (G-2), and the compound in molecule with more than at least two thioether group is episulfide resin (G-3) etc.
As described multi-functional epoxy compound (G-1), for example, can list: the EPICOAT828 that Mitsubishi chemical Co., Ltd manufactures, EPICOAT834, EPICOAT1001, EPICOAT1004, the Epiclon840 that DIC manufactures, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the Epotote YD-011 that company manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow ChemicalCompany manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Sumiepoxy ESA-011 that Sumitomo Chemical Co. Ltd. manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin, the EPICOAT YL903 that Mitsubishi Chemical manufactures, Epiclon152, Epiclon165 that DIC manufactures, Dongdu changes into Epotote YDB-400, the YDB-500 that company manufactures, the D.E.R.542 that Dow Chemical Company manufactures, Sumiepoxy ESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. manufactures, A.E.R.711, A.E.R.714 etc. (the being trade name) brominated epoxy resin that industrial group of Asahi Chemical Industry manufactures, the EPICOAT152 that Mitsubishi chemical Co., Ltd manufactures, EPICOAT154, the D.E.N.431 that DowChemical Company manufactures, D.E.N.438, the EpiclonN-730 that DIC manufactures, EpiclonN-770, EpiclonN-865, Dongdu changes into the Epotote YDCN-701 that company manufactures, YDCN-704, the EPPN-201 that chemical drug company of Japan manufactures, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumiepoxy ESCN-195X that Sumitomo Chemical Co. Ltd. manufactures, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry manufactures, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin, the Epiclon830 that DIC manufactures, Mitsubishi chemical Co., Ltd manufactures EPICOAT807, and Dongdu changes into (being trade name) bisphenol f type epoxy resin such as EpototeYDF-170, YDF-175, YDF-2004 that company manufactures, Dongdu change into company manufacture Epotote ST-2004, ST-2007, ST-3000(trade name) etc. bisphenol-A epoxy resin, the EPICOAT604 that Mitsubishi chemical Co., Ltd manufactures, Dongdu changes into the Epotote YH-434 that company manufactures, (being trade name) glycidyl amine type epoxy resin such as Sumiepoxy ELM-120 that Sumitomo Chemical Co. Ltd. manufactures, hydantoins type epoxy resin, DAICEL CHEMICALINDUSTRIES, (the being trade name) alicyclic epoxy resins such as the Celoxide2021 that LTD. manufactures, the YL-933 that Mitsubishi chemical Co., Ltd manufactures, (being trade name) trihydroxy benzene methylmethane type epoxy resin such as T.E.N., EPPN-501, EPPN-502 that Dow ChemicalCompany manufactures, Mitsubishi chemical Co., Ltd manufacture YL-6056, YX-4000, YL-6121(be trade name) etc. di-cresols type or bisphenol-type epoxy resin or their potpourri, the EBPS-200 that chemical drug company of Japan manufactures, the EPX-30 that Asahi Electro-Chemical Co. Ltd manufactures, the EXA-1514(trade name that DIC manufactures) etc. bisphenol-s epoxy resin, Mitsubishi chemical Co., Ltd manufacture EPICOAT157S(trade name) etc. bisphenol-A phenolic varnish type epoxy resin, (being trade name) the four hydroxyphenyl ethane type epoxy resin such as the EPICOAT YL-931 that Mitsubishi chemical Co., Ltd manufactures, (being trade name) hetero ring type epoxy resin such as the TEPIC that daily output chemical industrial company manufactures, the o-phthalic acid diglycidyl ester resins such as the Blemmer DGT that Nof Corp. manufactures, Dongdu changes into four glycidyl group xylenols ethane (the tetraglycidyl xylenoyl ethane) resins such as the ZX-1063 of company's manufacture, ESN-190, ESN-360 that chemical company of Nippon Steel manufactures, HP-4032, EXA-4750, the EXA-4700 etc. that DIC manufactures is containing Naphthol-based Epoxy Resin, HP-7200, the HP-7200H etc. that DIC manufactures has the epoxy resin of bicyclopentadiene skeleton, the glycidyl methacrylate such as CP-50S, the CP-50M copolymerization that Nof Corp. manufactures is epoxy resin, and the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivant (for example DAICEL CHEMICAL INDUSTRIES, the PB-3600 that LTD. manufactures etc.), CTBN modified epoxy (such as Dongdu changes into YR-102, the YR-450 etc. that company manufactures) etc., but be not limited to these.These epoxy resin can be used alone or in combination two or more.Particularly preferably bisphenol A type epoxy resin or their potpourri in them.
As aforementioned multifunctional oxetane compound (G-2), can list: two [(3-methyl-3-oxetanes ylmethoxy) methyl] ether, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, Isosorbide-5-Nitrae-bis-[(3-methyl-3-oxetanes ylmethoxy) methyl] benzene, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, their the multifunctional oxetanes class such as oligomer or multipolymer, and oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have the etherate of the resin of hydroxyl etc.In addition, also can list and there is the unsaturated monomer of oxetanes ring and the multipolymer of (methyl) alkyl acrylate etc.
As the compound (G-3) in described molecule with more than two cyclic thioether base, for example, can list: the bisphenol A-type episulfide resin YL7000 of Mitsubishi Chemical Ind's system etc.In addition, also can use and adopt same synthetic method the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin to be replaced as to sulphur atom and the episulfide resin that obtains etc.
In described molecule, there is the compounding amount of (G) Thermocurable composition of more than two ring-type (sulphur) ether, with respect to described carboxyl 1 equivalent containing carboxy resin (A), preferably ring-type (sulphur) ether is 0.6 ~ 2.0 equivalent, the more preferably scope of 0.8 ~ 1.5 equivalent.In molecule, have in the situation of compounding quantity not sufficient 0.6 of the Thermocurable composition (G) of more than two ring-type (sulphur) ether, remaining carboxyl in solder resist film, the reductions such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred.On the other hand, exceed in the situation of 2.0 equivalents, due to remaining low-molecular-weight ring-type (sulphur) ether in dry coating, be therefore coated with the reductions such as film strength, therefore not preferred.
Use in the situation of the Thermocurable composition (G) in described molecule with more than two ring-type (sulphur) ether, preferably contain thermal curing catalyst.As such thermal curing catalyst, for example, can list: imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-the imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzylamine, 4-methoxyl-N, N-dimethyl benzylamine, 4-methyl-N, the amines such as N-dimethyl benzylamine; The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds such as triphenylphosphine etc., in addition, as commercially available product, for example can list four countries and change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade name of imidazole compound) that industrial group manufactures, U-CAT3503N, U-CAT3502T (being the trade name of the blocked isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc. that SAN-APRO company manufactures.Be not particularly limited to these compounds, be epoxy resin thermal curing catalyst, oxetane compound thermal curing catalyst or promote at least any and the catalyzer reacting of carboxyl of epoxy radicals and oxetanyl, can use separately or mix two or more uses.In addition, also can use guanamines, methyl guanamines, benzoguanamine, melamine, 2,4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2, the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid addition product, the compound preferably these also being worked as adaptation imparting agent and aforementioned hot curing catalysts are used in combination.
other compositions
Alkali development-type photosensitive resin composition of the present invention further compounding phthalocyanine blue as required, phthalocyanine green, iodine is green, dual-azo yellow, crystal violet, titanium dioxide, carbon black, the known conventional colorants such as naphthalene blue-black, quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, the known conventional hot polymerization inhibitor such as phenothiazine, fine particle silica, organobentonite, the known conventional thickening agent such as polynite, silicon-type, fluorine system, the defoamers such as macromolecular and advection agent at least any, imidazoles system, thiazole system, the adaptation imparting agents such as triazole system, the known conventional additive kind such as silane coupling agent.
In the time forming the solder resist of printed circuit board (PCB), use alkali development-type photosensitive resin composition of the present invention, be adjusted to as required after the viscosity adapting to coating process, be coated on for example on the printed circuit board (PCB) that is pre-formed circuit by methods such as silk screen print method, heavy curtain print process, spraying process, rolling methods, for example by being dried processing with the temperature of approximately 60 ~ 100 DEG C, can form tack-free film as required.Then, see through the photomask of the exposing patterns that is formed with regulation, optionally utilize active ray to expose, by the alkaline aqueous solution unexposed portion of developing, can form corrosion-resisting pattern, and then, for example make its heat curing by the temperature that is heated to approximately 140 ~ 180 DEG C, thereby can promote the polymerization of curing reaction and the photoresist composition of described Thermocurable composition, improve the various characteristics such as thermotolerance, solvent resistance, acid resistance, resistance to hydroscopicity, PCT tolerance, adaptation, electrical characteristics of the overlay film against corrosion that obtains.
The aqueous alkali using during as above-mentioned development, can use the aqueous alkali of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.In addition,, as the radiation source for photocuring, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, semiconductor laser, Solid State Laser, xenon lamp or metal halide lamp etc. are suitable.
embodiment
Based on embodiment and comparative example, the present invention will be described in more detail, but protection scope of the present invention and embodiment thereof are not limited to these." part " in embodiment and comparative example or " % " are weight basis unless otherwise noted.By the method for following narration, carry out the character value test of the composition of the present embodiment.
synthesis example 1
Drop into 1 of carboxylic acid equivalent 86g/ equivalent to possessing gas introduction tube, stirring apparatus, condenser pipe, thermometer and dripping continuously in the reaction vessel of tap funnel of use, 378 parts of 86 parts of 4-cyclohexane dicarboxylic acids and bisphenol A type epoxy resins (Mitsubishi Chemical Ind's manufacture, EPICOAT828, epoxide equivalent 189g/ equivalent), under nitrogen atmosphere, under agitation at 110 DEG C, make its dissolving.Then, add 0.3 part of triphenylphosphine, the temperature in reaction vessel is warming up to 150 DEG C, maintain the temperature at 150 DEG C on one side, react approximately 90 minutes on one side, obtain the epoxy compound of epoxide equivalent 464g/ equivalent.Then the temperature in flask is cooled to 40 DEG C, adds 390 parts of carbitol acetates, heating for dissolving, adds 0.46 part of methylnaphthohydroquinone and 1.38 parts of triphenylphosphines, is heated to 95 ~ 105 DEG C, slowly drips 72 parts of acrylic acid, makes its reaction 16 hours.This resultant of reaction is cooled to 80 ~ 90 DEG C, adds 190 parts of tetrabydrophthalic anhydrides, make its reaction 8 hours.The nonvolatile component containing carboxyl photoresist that so operation obtains is 65%, and the acid number of solid constituent is 100mgKOH/g.Below this resin solution is called to varnish A.
synthesis example 2
In the four-hole boiling flask of stirrer and reflux condensing tube, drop into having that 214 parts of cresols phenolic resin varnish type epoxy resin EPICLON N-695(DIC manufacture, epoxide equivalent=214), add 103 parts of carbitol acetates, 103 parts of petroleum hydrocarbon solvents (the JapanEnergy Corporation manufacturer name of an article: Cactus Fines SF-01) heating for dissolving.Then, add as 0.1 part of quinhydrones of polymerization inhibitor with as 2.0 parts of triphenylphosphines of catalysts.This potpourri is heated to 95 ~ 105 DEG C, slowly drips 72 parts of acrylic acid, make its reaction 16 hours.The resultant of reaction obtaining is cooled to 80 ~ 90 DEG C, adds 91.2 parts of tetrabydrophthalic anhydrides and make its reaction 8 hours, cooling rear taking-up.The nonvolatile component containing carboxyl optical polymerism unsaturated compound that so operation obtains is 65%, and the acid number of solid constituent is 87.5mgKOH/g.Below, the solution of this resultant of reaction is called to varnish B.
Use described synthesis example 1-2 containing carboxy resin solution (varnish A, varnish B), with the various compositions shown in table 1 and ratio (mass parts) compounding, with after stirring machine premixed, grind mixingly with 3 rollers, prepare alkali development-type photosensitive resin composition.At this, with ERICHSEN company manufacture particle size analyzer carry out granulometry, the dispersion degree of the alkali development-type photosensitive resin composition obtaining is evaluated, result is below 15 μ m.
table 1
performance evaluation:
(1) resistance to blast hole
After each alkali development-type photosensitive resin composition of filling above-described embodiment 1-4 in the substrate of Φ 0.5,0.8mmt and comparative example 1-3, carry out photocuring and heat curing and obtain curing film, according to the test method of JIS C6481, use rosin series and water soluble flux by above-mentioned film be immersed in the scolder of 288 DEG C bathe in 10 seconds 3 times.Then the painting membrane stage of visualization TH part.Metewand is as follows.
Zero: in the TH500 hole of φ 500, film is completely not outstanding
5 of the outstanding less thaies of film in the TH500 hole of △: φ 500
×: in the TH500 hole of φ 500, giving prominence to of film is more than 5
(2) resistance to cavity
After each alkali development-type photosensitive resin composition of filling above-described embodiment 1-4 in the substrate of Φ 0.5,0.8mmt and comparative example 1-3, carry out photocuring and heat curing and obtain curing film, according to the test method of JIS C6481, use rosin series and water soluble flux by above-mentioned film be immersed in the scolder of 288 DEG C bathe in 10 seconds 3 times.Then carry out tape stripping, confirm the state of peeling off of TH periphery.Metewand is as follows.
Zero: in the TH500 hole of φ 500, do not produce cavity completely
In the TH500 hole of △: φ 500, produce 5 cavitys of less than
×: in the TH500 hole of φ 500, produce more than 5 cavity
(3) adaptation of the copper and in TH
After each alkali development-type photosensitive resin composition of filling above-described embodiment 1-4 in the substrate of Φ 0.5,0.8mmt and comparative example 1-3, carry out photocuring and heat curing, form cured coating film.Then confirm the profile status of substrate with optical microscope.Metewand is as follows.There is shown the schematic diagram of section shape.
Zero: the copper of TH and film are not peeled off etc. abnormal
×: copper and the film of TH are peeled off
(4) resistance to cracking line
After each alkali development-type photosensitive resin composition of embodiment 1-4 described in filling in the substrate of Φ 0.5,0.8mmt and comparative example 1-3, carry out photocuring and heat curing, form cured coating film.Then use the painting membrane stage of observation by light microscope TH part.Metewand is as follows.
Zero: in the TH500 hole of φ 500, there is no crackle completely
In the TH500 hole of △: φ 500, produce 5 crackles of less than
×: in the TH500 hole of φ 500, produce more than 5 crackle
By the table 2 that the results are shown in of above-mentioned each test.
Table 2
As known from the above, by being adjusted into the composition of embodiment 1-4, can obtain resistance to blast hole, resistance to cavity and with TH in the adaptation of copper and the photosensitive polymer combination of resistance to cracking line excellence.On the other hand, in comparative example 1, because the containing ratio of (E) talcum is low and adaptation is insufficient, its result, can not obtain with TH in the adaptation of copper.In comparative example 2, although (E) containing ratio of talcum is abundant, do not contain containing carboxy resin (A-1), therefore flexibility is insufficient, and its result can not obtain resistance to blast hole, resistance to cavity.In comparative example 3, owing to not containing (E) talcum, adaptation and flexibility are insufficient, its result, can not obtain with TH in adaptation and the resistance to cracking line of copper.
Claims (8)
1. an alkali development-type photosensitive resin composition, it is characterized in that, contain (A) containing carboxy resin, (B) Photoepolymerizationinitiater initiater, (C) diluting solvent, (D) in a part, there is the compound of more than two ethene unsaturated group and (E) talcum, contain carboxy resin as (A), the esterification product that contains the epoxy radicals that makes at least one bisphenol type epoxy compound (a) carry out esterification with unsaturated carboxylic acid (b) and to generate react with saturated or unsaturated multi-anhydride (c) and obtain containing carboxy resin (A-1), and more than 10 % by weight that (E) containing ratio of talcum is total amount and below 60 % by weight.
2. alkali development-type photosensitive resin composition according to claim 1, is characterized in that, it is for through hole (TH) filling purposes.
3. alkali development-type photosensitive resin composition according to claim 1, is characterized in that, it contains (F) filler except (E) talcum.
4. alkali development-type photosensitive resin composition according to claim 1, is characterized in that, it contains (G) Thermocurable composition.
5. alkali development-type photosensitive resin composition according to claim 1, is characterized in that, it is coated on copper and uses.
6. a dry film for photo-curable, is characterized in that, it is coated in carrier film and dry obtaining by the alkali development-type photosensitive resin composition described in any one of claim 1 ~ 5.
7. a solidfied material, is characterized in that, it solidifies following photocatalytic coating film to obtain, and described film is: the alkali development-type photosensitive resin composition described in any one of claim 1 ~ 5 is coated on copper and the dry film obtaining; Maybe this photosensitive polymer combination is coated in carrier film and dry, by the dry film lamination of gained photo-curable on copper and the film obtaining.
8. a printed circuit board (PCB), it is characterized in that, it possesses after following photocatalytic coating film is solidified and carries out heat curing and the solidfied material that obtains, and described film is: the alkali development-type photosensitive resin composition described in any one of claim 1 ~ 5 is coated on base material and the dry film obtaining; Maybe this photosensitive polymer combination is coated in carrier film and dry, by the dry film lamination of gained photo-curable on base material and the film obtaining.
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| CN201310038669.5A CN103969947B (en) | 2013-01-31 | 2013-01-31 | Alkali development-type photosensitive resin composition, its dry film and solidfied material thereof and use it and the printed circuit board (PCB) that forms |
| TW102118413A TWI516869B (en) | 2013-01-31 | 2013-05-24 | An alkali developing type photosensitive resin composition, a dry film thereof and a cured product thereof, and a printed circuit board formed using one another |
| KR1020157020481A KR101726114B1 (en) | 2013-01-31 | 2013-08-09 | Alkali development type photosensitive resin composition, dry film and cured product thereof, and printed circuit board formed by using same |
| JP2015555545A JP6118426B2 (en) | 2013-01-31 | 2013-08-09 | Alkali-developable photosensitive resin composition, dry film and cured product thereof, and printed wiring board formed using them |
| PCT/CN2013/081148 WO2014117496A1 (en) | 2013-01-31 | 2013-08-09 | Alkali development type photosensitive resin composition, dry film and cured product thereof, and printed circuit board formed by using same |
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| CN107003604A (en) * | 2014-10-15 | 2017-08-01 | 奇美实业股份有限公司 | Photosensitive resin composition, the manufacture method of colored filter, colored filter and liquid crystal display device |
| CN107490936A (en) * | 2016-06-09 | 2017-12-19 | 株式会社田村制作所 | The forming method of cured coating film |
| CN109976092A (en) * | 2017-12-27 | 2019-07-05 | 太阳油墨（苏州）有限公司 | Hardening resin composition, dry film, solidfied material and printed circuit board |
| CN110999554A (en) * | 2017-08-09 | 2020-04-10 | 互应化学工业株式会社 | Method for manufacturing multilayer printed wiring board and multilayer printed wiring board |
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| CN113196171A (en) * | 2018-12-19 | 2021-07-30 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
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| CN107003604A (en) * | 2014-10-15 | 2017-08-01 | 奇美实业股份有限公司 | Photosensitive resin composition, the manufacture method of colored filter, colored filter and liquid crystal display device |
| CN107003604B (en) * | 2014-10-15 | 2020-08-11 | 奇美实业股份有限公司 | Photosensitive resin composition, method for producing color filter, and liquid crystal display device |
| CN107490936A (en) * | 2016-06-09 | 2017-12-19 | 株式会社田村制作所 | The forming method of cured coating film |
| CN110999554A (en) * | 2017-08-09 | 2020-04-10 | 互应化学工业株式会社 | Method for manufacturing multilayer printed wiring board and multilayer printed wiring board |
| CN110999554B (en) * | 2017-08-09 | 2021-05-18 | 互应化学工业株式会社 | Method for manufacturing multilayer printed wiring board and multilayer printed wiring board |
| CN109976092A (en) * | 2017-12-27 | 2019-07-05 | 太阳油墨（苏州）有限公司 | Hardening resin composition, dry film, solidfied material and printed circuit board |
| CN111417901A (en) * | 2018-10-30 | 2020-07-14 | 互应化学工业株式会社 | Resin composition for forming insulating film, method for producing resin composition for forming insulating film, dry film, printed wiring board, and method for producing printed wiring board |
| CN113196171A (en) * | 2018-12-19 | 2021-07-30 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN113196171B (en) * | 2018-12-19 | 2024-04-23 | 太阳控股株式会社 | Curable resin composition, dry film, cured product, and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150102105A (en) | 2015-09-04 |
| WO2014117496A1 (en) | 2014-08-07 |
| KR101726114B1 (en) | 2017-04-11 |
| JP6118426B2 (en) | 2017-04-19 |
| TWI516869B (en) | 2016-01-11 |
| JP2016513268A (en) | 2016-05-12 |
| CN103969947B (en) | 2016-05-04 |
| TW201430492A (en) | 2014-08-01 |
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